CN101914250B - Preparation method of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability - Google Patents
Preparation method of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability Download PDFInfo
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- CN101914250B CN101914250B CN2010102625964A CN201010262596A CN101914250B CN 101914250 B CN101914250 B CN 101914250B CN 2010102625964 A CN2010102625964 A CN 2010102625964A CN 201010262596 A CN201010262596 A CN 201010262596A CN 101914250 B CN101914250 B CN 101914250B
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Abstract
The invention discloses a preparation method of an environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability, comprising the following steps of: (1) adding 100 parts by weight of polyvinyl chloride and 100-2000 parts by weight of lanthanum-tin composite stabilizers to a high-speed mixer for mixing to 50-80 DEG C, discharging and adding to a cold mixer for mixing, cooling the temperature to 40 DEG C, and then adding 100-2000 parts by weight of acrylate processing aids, 100-2000 parts by weight of internal lubricants, 50-500 parts by weight of external lubricants and 100-5000 parts by weight of nano rigid particles to the mixture for fully mixing to obtain a polyvinyl chloride composite; and (2) adding the polyvinyl chloride composite to a reactor, heating to fuse the polyvinyl chloride composite, then stirring for uniformly mixing, and then cooling, granulating and drying. The obtained modified polyvinyl chloride master batch can be conveniently blended with common polyvinyl chloride for granulation so that the finally obtained modified polyvinyl chloride has favorable processing fluidity, heat stability and mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Background technology
Polyvinyl chloride is one of general-purpose plastics of using always, have fire-retardant, chemical proofing is high, physical strength and advantage such as electrical insulating property is good, price is low, Application Areas is wide, be widely used in aspects such as tubing, bar, film, material of construction, its output occupies second of world's resin yield.But polyvinyl chloride especially rigid polyvinyl chloride has shortcomings such as flowability is poor, poor heat stability, poor heat resistance, poor toughness, has limited its use.
The modification approach of polyvinyl chloride mainly comprises chemical modification and physically modified.Chemical modification is carried out modification by methods such as copolymerization, graft reactions to polyvinyl chloride exactly.Chemical modification is obvious to PVC modified effect, has relatively high expectations but generally technology is controlled, and step is complicated.The second approach of modified polyvinyl chloride is a physically modified, promptly by adding various auxiliary agents or carrying out blend and improve its performance.This method is simple, is the method for modifying that is widely adopted.
January 10 nineteen ninety, disclosed Chinese patent CN1038660A disclosed " filling type polyviny/chloride flow modifier and its producing ", and this patent adds the particles of packing material through four layers of coating in pure PVC, had improved the processing characteristics of rigid polyvinyl chloride.On July 5th, 2006, disclosed Chinese patent CN1796426A disclosed " making method of resin in high flowage dedicated to polyvinyl chloride ", it is resin dedicated with after water, vinylchlorid, water soluble dispersing agent, oil-soluble initiator and pH regulator agent and chain-transfer agent uniform mixing and the reaction to change polyvinyl chloride, add terminator, separation, drying obtain resin in high flowage dedicated to polyvinyl chloride, this resin dedicated when the injection moulding pipe fitting flowability fine, can make material be full of mould fast, and products surface quality is good.On October 7th, 2009, disclosed Chinese patent CN100547027C disclosed " PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier ", this properties-correcting agent is the nucleocapsid structure multipolymer, stratum nucleare carries out emulsion polymerization by butyl acrylate and linking agent, slightly acidic hole enlargement agent and forms, shell at first is to continue letex polymerization by methyl methacrylate and vinylbenzene on stratum nucleare, methyl methacrylate coats separately and forms second shell then, adds the acrylic ester impact-resisting modifier separant after polymerization is finished in the emulsion.This patent has solved the compatibility problem of anti-impact ACR and PVC, anti-impact ACR is dispersed in the PVC particle fast, effectively the toughening PVC goods.On September 16th, 2009, disclosed Chinese patent CN101531793A disclosed " heat-resistant polyvinyl chloride alloy material and preparation method thereof ", this alloy is made up of polyvinyl chloride matrix, heat-proof modifier, thermo-stabilizer, lubricant, filler, impact modifier and processing aid, this alloy has improved the consistency of polyvinyl chloride and heat stable resin, solved thermal stability of polyethylene can raising and intensity and flexible contradiction, prepared the polyvinyl chloride engineering plastics of high heat-resisting, high strength and high tenacity.On October 30th, 1996, disclosed Chinese patent CN1134436 disclosed " improving the method for thermal stability of polyethylene ", made thermoplastic compounds based on polyvinyl chloride, its thermotolerance height has mechanical property preferably simultaneously, particularly shock resistance height, good with ageing-resistant performance.On August 10th, 2005, disclosed Chinese patent CN1651505A disclosed a kind of heat-resisting smoke-inhibiting PVC composition and preparation method thereof, said composition adopts polynary compounding technology to improve the heat-resisting and toughness defect of insufficient of polyvinyl chloride, have heat-resisting, fire-retardant, press down cigarette, multiple excellent properties such as weather-proof.As seen existing research adopt chemical process and physical method all can effectively improve the processing fluidity and the mechanical property of polyvinyl chloride.Wherein the chemical modification effect is obvious, but often preparation technology's condition control ratio is harsh, and technical requirements is higher; Physical method is simple and easy to do, but the adding of multiple properties-correcting agent, tends to occur with the system consistency relatively poor and cause the problem of mechanical properties decrease.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability is provided.Adopt the mechanochemical method preparation environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability that combines with the physical blending method, this modified polyvinyl chloride master batch is applied to can effectively improve its processing fluidity and thermostability in the rigid polyvinyl chloride.
Environment-friendly type is the high preparation method who flows the high thermal stability modified polyvinyl chloride master batch comprise the steps:
1) 100 weight part polyvinyl chloride, 100-2000 weight part lanthanum tin one package stabilizer are added in the high-speed mixer, be mixed to 50-80 ℃, discharging adds and mixes in the cold mixer and cooling, after temperature is reduced to 40 ℃, add 100-2000 parts by weight of acrylic acid ester class processing aid, 100-2000 weight part internal lubricant, 50-500 weight part external lubricant, 100-5000 weight part nano redigity particle, thorough mixing obtains polyvinyl chloride composite;
2) polyvinyl chloride composite is added in the reactor, be heated to 140-200 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 5-60 minute, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
The polymerization degree of described polyvinyl chloride is 300-2500.Described lanthanum tin one package stabilizer is the mixture of stearic acid lanthanum and methyl mercaptan organotin, and the weight ratio of stearic acid lanthanum and methyl mercaptan organotin is 8: 2-4: 6.Described internal lubricant is selected from saturated hydrocarbons lubricant, fatty acid lubricant or metallic soap series lubricant agent.Described external lubricant is oxidized polyethlene wax or paraffin.Described nano redigity particle is the nano silicon that the nano-calcium carbonate handled of stearic acid or stearic acid were handled, particle diameter 30-200 nanometer.
The present invention compared with prior art, the beneficial effect that has is:
1) by new complete processing polyvinyl chloride and auxiliary agent are carried out the power chemical treatment and prepare modified master batch, strengthened the dispersion of nano redigity particle in polyvinyl chloride composite, improved the consistency of polyvinyl chloride and auxiliary agent;
2) adopt lanthanum tin one package stabilizer, thermostable effect is obvious, environment-protecting asepsis, and the stearic acid lanthanum can increase the flowability of system;
3) this master batch plasticizer-containing is not effectively regulated processing fluidity by the stearic acid lubricant quantity, has overcome in the past the easily shortcoming of migration of softening agent additive;
4) provide a kind of and prepared the method for the high high thermal stability rigid polyvinyl chloride that flows, reduced the preparation section of polrvinyl chloride product by the master batch two-step approach.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
100 weight part polyvinyl chloride, 100 weight part lanthanum tin one package stabilizers are added in the high-speed mixer, be mixed to 50 ℃, discharging adds and mixes in the cold mixer and cooling.After treating that temperature of charge is reduced to 40 ℃, add 100 parts by weight of acrylic acid ester class processing aids, 100 weight part internal lubricants, 50 weight part external lubricants, 100 weight part nano redigity particles, thorough mixing obtains polyvinyl chloride composite.Polyvinyl chloride composite is added in the reactor, be heated to 140 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 5 minutes, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Embodiment 2
100 weight part polyvinyl chloride, 2000 weight part lanthanum tin one package stabilizers are added in the high-speed mixer, be mixed to 80 ℃, discharging adds and mixes in the cold mixer and cooling.After treating that temperature of charge is reduced to 40 ℃, add 2000 parts by weight of acrylic acid ester class processing aids, 2000 weight part internal lubricants, 500 weight part external lubricants, 5000 weight part nano redigity particles, thorough mixing obtains polyvinyl chloride composite.Polyvinyl chloride composite is added in the reactor, be heated to 200 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 60 minutes, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Embodiment 3
100 weight part polyvinyl chloride, 1000 weight part lanthanum tin one package stabilizers are added in the high-speed mixer, be mixed to 60 ℃, discharging adds and mixes in the cold mixer and cooling.After treating that temperature of charge is reduced to 40 ℃, add 1000 parts by weight of acrylic acid ester class processing aids, 1000 weight part internal lubricants, 300 weight part external lubricants, 3000 weight part nano redigity particles, thorough mixing obtains polyvinyl chloride composite.Polyvinyl chloride composite is added in the reactor, be heated to 170 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 30 minutes, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Embodiment 4
100 weight part polyvinyl chloride, 500 weight part lanthanum tin one package stabilizers are added in the high-speed mixer, be mixed to 70 ℃, discharging adds and mixes in the cold mixer and cooling.After treating that temperature of charge is reduced to 40 ℃, add 500 parts by weight of acrylic acid ester class processing aids, 500 weight part internal lubricants, 200 weight part external lubricants, 2000 weight part nano redigity particles, thorough mixing obtains polyvinyl chloride composite.Polyvinyl chloride composite is added in the reactor, be heated to 160 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 20 minutes, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Embodiment 5
100 weight part polyvinyl chloride, 1500 weight part lanthanum tin one package stabilizers are added in the high-speed mixer, be mixed to 70 ℃, discharging adds and mixes in the cold mixer and cooling.After treating that temperature of charge is reduced to 40 ℃, add 1500 parts by weight of acrylic acid ester class processing aids, 1500 weight part internal lubricants, 400 weight part external lubricants, 4000 weight part nano redigity particles, thorough mixing obtains polyvinyl chloride composite.Polyvinyl chloride composite is added in the reactor, be heated to 190 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 50 minutes, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability.
Master batch that each embodiment is made and common polyvinyl chloride by weight 10/100 in conical double screw extruder and injection moulding machine through extrude, injection moulding, the performance test data of the modified hard polyethylene chloride product that finally obtains sees Table 1.
Table 1
Claims (5)
1. the preparation method of the high high thermal stability modified polyvinyl chloride master batch that flows of environment-friendly type is characterized in that comprising the steps:
1) 100 weight part polyvinyl chloride, 100-2000 weight part lanthanum tin one package stabilizer are added in the high-speed mixer, be mixed to 50-80 ℃, discharging adds and mixes in the cold mixer and cooling, after temperature is reduced to 40 ℃, add 100-2000 parts by weight of acrylic acid ester class processing aid, 100-2000 weight part internal lubricant, 50-500 weight part external lubricant, 100-5000 weight part nano redigity particle, thorough mixing obtains polyvinyl chloride composite;
2) polyvinyl chloride composite is added in the reactor, be heated to 140-200 ℃, make the polyvinyl chloride composite fusion, stir then and made it to mix in 5-60 minute, cooling, pelletizing, drying obtain environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability;
Described nano redigity particle is the nano silicon that the nano-calcium carbonate handled of stearic acid or stearic acid were handled, particle diameter 30-200 nanometer.
2. the preparation method of a kind of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability according to claim 1 is characterized in that, the polymerization degree of described polyvinyl chloride is 300-2500.
3. the preparation method of a kind of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability according to claim 1, it is characterized in that, described lanthanum tin one package stabilizer is the mixture of stearic acid lanthanum and methyl mercaptan organotin, and the weight ratio of stearic acid lanthanum and methyl mercaptan organotin is 8: 2-4: 6.
4. the preparation method of a kind of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability according to claim 1 is characterized in that, described internal lubricant is selected from saturated hydrocarbons lubricant, fatty acid lubricant or metallic soap series lubricant agent.
5. the preparation method of a kind of environment-friendly modified polyvinyl chloride master batch with high fluidity and heat stability according to claim 1 is characterized in that, described external lubricant is oxidized polyethlene wax or paraffin.
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| CN102417676B (en) * | 2011-11-16 | 2013-09-11 | 山东瑞丰高分子材料股份有限公司 | Composite stabilizing agent for transparent polyvinyl chloride (PVC) material and preparation method thereof |
| CN104816396B (en) * | 2015-04-02 | 2017-01-04 | 晋江鑫邦新材料科技有限公司 | A kind of method utilizing footwear material waste material to prepare Masterbatch |
| JP6222187B2 (en) * | 2015-08-19 | 2017-11-01 | コニカミノルタ株式会社 | Solid lubricant, image forming apparatus and image forming method |
| CN105602159A (en) * | 2016-03-23 | 2016-05-25 | 陈逸君 | PVC master batch and preparation method thereof |
| CN110372975A (en) * | 2019-09-02 | 2019-10-25 | 百尔罗赫塑料添加剂（江苏）有限公司 | It is a kind of for improving the environmentally friendly auxiliary agent and preparation method thereof of PVC injection molding pipe part performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717466A (en) * | 2009-11-12 | 2010-06-02 | 浙江大学 | Polyvinyl chloride processing aid and preparation method thereof |
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| CN101717466A (en) * | 2009-11-12 | 2010-06-02 | 浙江大学 | Polyvinyl chloride processing aid and preparation method thereof |
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| Title |
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| 李国立等.稀土复合热稳定剂对聚氯乙烯性能影响研究.《现代塑料加工应用》.2004,第16卷(第2期),15-18. * |
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